Paper published as part of the special topic on Interfacial Electrochemistry and Photo(electro)catalysis
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Water oxidation is pivotal in biological photosynthesis, where it is catalyzed by a protein-bound metal complex with a Mn4Ca-oxide core; related synthetic catalysts may become key components in non-fossil fuel technologies.
The emergence of disordered metal oxides as electrocatalysts for the oxygen evolution reaction and reports of amorphization of crystalline materials during electrocatalysis reveal a need for robust structural models for this class of materials. Here we apply a combination of low-temperature X-ray absorption spectroscopy and time-resolved in situ X-ray absorption spectroelectrochemistry to analyze the structure and electrochemical properties of a series of disordered iron-cobalt oxides. We identify a composition-dependent distribution of di-μ-oxo bridged cobalt–cobalt, di-μ-oxo bridged cobalt–iron and corner-sharing cobalt structural motifs in the composition series. Comparison of the structural model with (spectro)electrochemical data reveals relationships across the composition series that enable unprecedented assignment of voltammetric redox processes to specific structural motifs. We confirm that oxygen evolution occurs at two distinct reaction sites, di-μ-oxo bridged cobalt–cobalt and di-μ-oxo bridged iron–cobalt sites, and identify direct and indirect modes-of-action for iron ions in the mixed-metal compositions.
CO reduction is of significant interest for the production of nonfossil fuels. The reactivity of eight Cu foams with substantially different morphologies was comprehensively investigated by analysis of the product spectrum and in situ electrochemical spectroscopies (X-ray absorption near edge structure, extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, and Raman spectroscopy). The approach provided new insight into the reactivity determinants: The morphology, stable Cu oxide phases, and *CO poisoning of the H formation reaction are not decisive; the electrochemically active surface area influences the reactivity trends; macroscopic diffusion limits the proton supply, resulting in pronounced alkalization at the CuCat surfaces (operando Raman spectroscopy). H and CH formation was suppressed by macroscopic buffer alkalization, whereas CO and C H formation still proceeded through a largely pH-independent mechanism. C H was formed from two CO precursor species, namely adsorbed *CO and dissolved CO present in the foam cavities.
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